Materials Research Bulletin 40 (2005) 529536

www.elsevier.com/locate/matresbu

Microwave synthesis of yttria stabilized zirconia

Lionel Combemale, Gilles Caboche*, Didier Stuerga, Denis Chaumont
Laboratoire de Recherches sur la Reactivite des Solides LRRS/UMR 5613 CNRS,
Universite de Bourgogne, 9 Avenue Alain Savary BP47870, 21078 Dijon Cedex, France

Received 8 July 2003; received in revised form 25 October 2004; accepted 29 October 2004

Abstract

Yttria stabilised zirconia (YSZ) nanocrystals, with a mean size between 5 and 10 nm, were prepared by
microwave flash synthesis. Flash synthesis was performed in alcoholic solutions of yttrium, zirconium chloride and
sodium ethoxide (EtONa) using a microwave autoclave (RAMO system) specially designed by authors. Energy
dispersive X-ray analysis (EDX), X-ray powder diffraction (XRD), BET adsorption technique, photon correlation
spectroscopy (PCS) transmission and scanning electron microscopy (TEM and SEM) are used to characterized
these nanoparticles. Compared with conventional synthesis, nanopowders can be produced in a short period (e.g.
10 s), both high purity and stoechiometric control are obtained. Nevertheless, this mean of production is more
cheaper and much faster than the ones commonly used to produce yttria stabilized zirconia (YSZ) by conventional
solgel techniques.
# 2004 Published by Elsevier Ltd.
Keywords: A. Nanostructures; B. Chemical synthesis; C. X-ray diffraction; C. Electron microscopy; D. Ionic conductivity

1. Introduction

Yttria stabilized zirconia (YSZ) is usually used as electrolyte in the technology of solid oxide fuel cell
(SOFC). It exhibits an appropriate ionic conductivity [1], has a good chemical stability in oxidizing or
reducing environment [2] and is not reactive to electrode materials for SOFC applications [3,4].
Various techniques have been used to synthesize this compound: solid state reaction [5], hydrothermal
route [6], polymerization route [2] and solgel method [7]. Advantages and limitations of these

* Corresponding author. Tel.: +3 80 39 61 53; fax: +3 80 39 61 32.

E-mail address: gilles.caboche@u-bourgogne.fr (G. Caboche).

0025-5408/$ see front matter # 2004 Published by Elsevier Ltd.

doi:10.1016/j.materresbull.2004.10.024
530 L. Combemale et al. / Materials Research Bulletin 40 (2005) 529536

techniques have been discussed in literature [8]. Typical drawbacks of conventional methods of
preparation are inhomogeneity, varied particle size distribution and poor reactivity when fine spherical
particles, with narrow size distribution, are desirable for producing ceramics with enhanced reliability. As
a common point, morphology of nanocrystals and control of chemical composition appear to be crucial
for industrial applications.
Microwave-assisted synthesis is a new way to produce inorganic compounds because microwave
heating is an in situ mode of energy conversion very attractive for chemists. The RAMO system (french
acronym of Reacteur Autoclave MicroOnde) is an original microwave device designed by our research
team [9]. This device is able to produce rapid bulk heating. Due to strong thermal gradients induced by
microwave heating, strong stirring occurs for liquids leading to thermal uniformity of heated medium.
Hence, it combines advantages of forced hydrolysis (homogeneous precipitation) and very fast heating
rate. RAMO system has allowed production of various nanomaterials [1017].
Only a few publications reported microwave synthesis of zirconia [12,1821]. Nanosized monoclinic
zirconia has been produced by flash-synthesis with RAMO System [12]. These operating conditions
using acidic aqueous solutions of zirconium chloride had tremendous drawback. It is not possible to
associate other metal as yttrium or cerium with zirconium in order to obtain solid solutions. Conse-
quently, the purpose of this work is to synthesize YSZ powders with narrow size distribution close to
10 nm. Starting materials are zirconium and yttrium chloride with sodium ethoxide (EtONa). The use of
sodium ethoxide as mineralizer is based on our previous works upon iron metal/oxide nanocomposites
[13,16]. The nominal composition chosen for the present study is (ZrO2)0.92(Y2O3)0.08O2 leading to cubic
phase of zirconia. This flash-synthesis process is called microwave forced hydrolysis.

2. Experimental

2.1. Operating conditions

All the chemicals products, anhydrous zirconium chloride (ZrCl4, Acros Organics, purity >98%),
yttrium chloride (YCl3
6H2O, Acros Organics, purity >99,9%), sodium ethoxide (EtONa, Aldrich, 96%)
and ethanol (Prolabo, Normapur, 96%) were reagents grade used without further purification. Initial
concentrations were chosen to obtain a yttrium(III) to zirconium(IV) ratio chosen in relation to
crystallographic phase expected: tetragonal (down to 7 mol% of Y2O3) and cubic (from 7 mol%).
The general flowchart of the operating conditions is described by the Fig. 1. The solution 1 was prepared
by mixing appropriate amounts of zirconium and yttrium chloride in ethanol. The zirconium and yttrium
concentration are fixed at 0.25 M (22.8 g l1) and 0.04 M (3.6 g l1) respectively in order to obtain cubic
phase: ratio Y2O3 to ZrO2 close to 15% in weight. The concentration of the sodium ethanoate solution
(solution 2) is equal to 1M (68 g l1). These solutions 1 and 2 were vigorously mixed and stirred in the
RAMO system (Fig. 2) whereas a precipitate appears.
This original experimental device is constituted of a microwave applicator associated with an autoclave.
Compared to a domestic oven or commercial device (CEM or Millestone), our microwave oven allows a
higher electric field strength for the heated sample. The microwave generator used is a continuous wave
system with a power up to 2 kW (2.45 GHz). The autoclave is made with polymer materials which are
microwave transparent, chemically inert and sufficiently strong to accommodate the pressure induced. The
reactants are placed in a Teflon flask inserted within a polyetherimide flask. A fiber-optic thermometry
 L. Combemale et al. / Materials Research Bulletin 40 (2005) 529536 531

Fig. 1. Flowsheet of the YSZ powder preparation by the microwave process.

system, a pressure transducer and a manometer allow to measure simultaneously the temperature and the
pressure within the reactor. Temperature measurements under microwave heating are very difficult and non-
perturbing temperature sensor could be used. The system is controlled by pressure. The microwave power is
adjusted in order to allow constant pressure within the vessel. A pressure release valve incorporated permits to
use this experimental device routinely and safely. Furthermore, we can introduce an inert gas such as argon
within the reactor to avoid sparking risk with flammable solvents as ethanol. This experimental device is able
to raise the temperature from ambient to 200 8C in less than 20 s (the pressure is close to 1.2 MPa and the
heating rate is close to 5 8C/s). More details about microwave devices, microwave heating and non-perturbing
temperature sensors could be found in [9].
This reactor was quickly sealed and an argon pressure introduced (0.4 MPa). Microwave treatments
were performed with RAMO. The treatment was decomposed in two steps. During the first step, the

Fig. 2. Presentation of microwave autoclave reactor RAMO.

532 L. Combemale et al. / Materials Research Bulletin 40 (2005) 529536

Fig. 3. Evolution of temperature and pressure vs. time. Initial power: 1 kW.

microwave power (1 kW) is applied until the pressure reaches a threshold value of 1 MPa. This pressure
corresponds to a temperature close to 160 8C. During the second step, this pressure threshold was kept by
monitoring the microwave power. The heating rate is close to 10 8C/s. The Fig. 3 illustrates the
relationship between temperature and pressure generated within the reactor for ethanol and the reactive
medium used: ethanol reaches a temperature of 160 8C and a pressure of 1.0 MPa in 40 s for a microwave
power of 1 kW. The reactive medium leads to a higher heating rate since metallic salts and sodium
ethoxide increase the dielectric losses.
Microwave treatment time chosen is equal to 2 min. After this microwave treatment, powders were
centrifuged and washed with distilled water in order to eliminate sodium and chloride ions. They were
dried at room temperature. Finally, annealing treatment at 300 8C, 600 8C, 800 8C and 1200 8C was made
to induce growing of crystals in order to reveal cubic phase. Typically, 350 mg of nanosized YSZ is
obtained in one step.

2.2. Characterization

The X-ray powder diffraction (XRD) patterns of the samples, as prepared or heated at different
temperatures, were recorded using a SIEMENS D-5000 diffractometer with Cu-Ka radiation source for
phase identification. The standard BET technique was employed to measure the specific surface area, of
YSZ powder as prepared, using an AUTOSORB 1 QUANTA CHROME device and nitrogen as
adsorption gas. Chemical analysis was done by using OXFORD INSTRUMENT EDX. Granulometric
distributions was measured by photon correlation spectroscopy (PCS) with the spectrometer 7032
MALVERN INSTRUMENTS. Finally, scanning electron microscopy (JEOL JSM 6400) and transmis-
sion electron microscopy (JEOL 2010 F) were used to estimate particle size, nature of agglomerates and
morphology of the final YSZ powder.

3. Results

Table 1 compares Y2O3 and ZrO2 mol% between initial mixture, raw powder and after annealing at
800 8C for 2 h. Powders composition is determined by EDX analysis. Despite microwave and annealing
 L. Combemale et al. / Materials Research Bulletin 40 (2005) 529536 533

Table 1
Percentage by mol of zirconia and yttria in the initial solution and in YSZ powders after microwave treatment and subsequent
thermal treatment in air at 800 8C
ZrO2 Y2O3
Initial reactants in solution 1 (mol%) 92.5  0.2 7.4  0.2
YSZ powder after microwave treatment (mol%) 92.2  0.9 7.7  0.7
YSZ powder after heat treatment at 800 8C in air for 2 h (mol%) 92.0  0.9 8.0  0.6

treatments, the ratio yttrium to zirconium of the initial mixture is kept within solid solution of zirconia
and yttria. Hence, these operating conditions allow composition control of powder produced in relation to
chloride precursor ratio of within initial solution. EDX analysis shows that no sodium or chlorine is
present in the powders.
To determine the morphology powder have been, firstly, analyzed by X-ray diffraction. The XRD
patterns are shown, Fig. 4, for microwave raw powder and after annealing treatment at 300 8C, 600 8C,
800 8C and 1200 8C. If the initial mixture of solutions 1 and 2 is not microwave treated, yield
precipitation is very slight (<5%) and a mixture of zirconium and yttrium oxides are obtained. The
nanometric size of the particles leads to strong broadening of X-ray lines and despite careful analysis of
XRD patterns of raw powder, it is difficult to conclude about nature of the crystallographic phase
produced. However, Bragg reflections intensities of cubic phase are observed after annealing treatment.
The XRD pattern after heat treatment at 300 8C shows a slight increase of crystallinity as compared to the
raw microwave powder and X-ray lines become thinner and thinner with temperature increasing (up to
600 8C) due to strong growing of crystal size. Crystallinity of raw microwave powder was found to be
poor compared to those obtained after annealing treatment. Absences of either monoclinic zirconia or
segregated yttrium compounds demonstrate homogeneous dispersion of yttrium within powder.

Fig. 4. X-ray patterns of YSZ powders calcinated at various temperatures for 2 h in air. A = 25 8C (before heat treatment);
B = 300 8C, C = 600 8C, D = 800 8C E = 1200 8C.
534 L. Combemale et al. / Materials Research Bulletin 40 (2005) 529536

Fig. 5. (a) TEM micrograph in dark field (b) TEM micrograph in bright field.

The surface area of raw microwave powder was measured by BET technique, after bakeout at 40 8C
for 72 h. The nitrogen adsorption at 77 K leads to a relatively high value (228 m2 g1). Assuming
spheroids particles, a mean value of diameter close to 5 nm can be estimated using Eq. (1). TEM
micrographs displayed by the Fig. 5 confirm the nanostructured features of samples produced. The
crystallites exhibit mean size lower than 20 nm (a) whereas submicronic aggregates which look like
snowflakes are observed (b). The mean size of these aggregates is close to 150 nm. These results
corroborate the strong broadening of X-ray lines observed.
6
D (1)
rS
where D is the diameter in mm, r the volumic mass in g cm3 and S is the specific area in m2 g1.
To corroborate the size of these agglomerates, measurements by photon correlation spectroscopy
(PCS) were carried out. A piece of powder was dispersed into water under ultrasonic device during
30 min. A narrow size distribution, Fig. 6, centered at 120 nm was obtained.

Fig. 6. PCS size distribution of the Microwave YSZ powder in dispersion in water.
 L. Combemale et al. / Materials Research Bulletin 40 (2005) 529536 535

4. Discussion, conclusion

According to these data, nanosized YSZ could be produced by microwave flash synthesis with RAMO
system. Powders with high specific surface are produced at low temperature (160 8C) and short heating
time (2 min). Grain size and crystallinity could be increase by further thermal annealing. Moreover, the
stability of cubic phase is maintained up to 1200 8C. Operating conditions use zirconium and yttrium
chlorides alcoholic solutions associated with sodium ethoxide. These conditions are cheaper and more
rustic comparing to classical solgel conditions using other alkoxides. Nevertheless, they allow the
control of yttrium to zirconium ratio within powder produced.
Among papers reported microwave synthesis of zirconia, Komarneni et al. [18] have produced
zirconia submicron powder (monoclinic) from aqueous zirconyl nitrate solutions at 164 8C for 2 h using
KOH as mineralizer. Among crystalline unary oxide produced by these authors, zirconia do not show
evidence of precipitation kinetic enhancement. According to their results, crystallization time for pure
zirconia is around 2 h for both microwave and conventional methods. Bellon et al. [12] contrary to these
results have observed very fast microwave forced hydrolysis of zirconium tetrachloride aqueous
solutions. Operating conditions using RAMO system and acidic aqueous solutions leads to monodisperse
zirconia nanoparticles (monoclinic). The induction period of 20 h usually observe for conventional
heating mode is reduce to few seconds. According to Khollan et al. [21] using aqueous solutions of
zirconyl nitrate and yttrium chloride and operating conditions close to ours (200 8C, microwave heating
time close to 5 min), crystallization kinetics was faster for YSZ because yttrium might enhance
crystallization of YSZ phase. Homogeneous dispersion of yttrium in YSZ powder is also observed.
It seems that microwave core heating allows volumetric nucleation in relation to temperature superior to
100 8C. In our case, sodium ethoxide used instead of potassium hydroxide enhance crystallization kinetic
and surface area (228 compare to 125 m2 g1). This value of surface area seems the higher obtained
whatever the method of preparation: conventional or microwave heating [8]. Due to this high surface area
and high temperature stability of cubic phase, powder produced with RAMO system could have catalytic
properties enhanced compared to conventional powder. This point should be tested in future. Aggregation
during precipitation from a supersaturated solution is the general mechanism for particles growth.
Despite nanosized crystals, powders are systematically composed of several aggregation levels over-
lapped and typical size of lumps is close to micrometer (Fig. 7). According to value of surface area, it
seems that aggregation level of microwave powder is quite different comparing to conventional powders.
This second point could be also examined in the future.

Fig. 7. Schematic morphology of YSZ powder synthesized by microwave technique.

536 L. Combemale et al. / Materials Research Bulletin 40 (2005) 529536

Acknowledgements

The authors acknowledge financial support from Gaz de France and are grateful to M.G. Bertrand for
his keen interest.
The authors wish to gratefully acknowledge V. Potin for all the TEM micrographs.

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